The presence of halogens has an adverse effect on the zinc extraction process through electrowinning, the last phase of the RLE (Roasting, Leaching and Electrowinning) zinc extraction route. Fluoride (F⁻) may be present as calcium fluoride (CaF₂) and this is, for example, the case in double leached Waelz oxide (DLWO). Efficient removal of F⁻ from primary and secondary raw materials for zinc extraction results in a simplified process and increases flexibility in the selection of raw materials. Understanding of the solubility behavior of pure CaF₂ can give valuable information on treatment for maximized halogen removal. Dissolution of CaF₂ was studied with the addition of sodium carbonate (Na₂CO₃) and sodium bicarbonate (NaHCO₃). Dissolution studies were combined with thermodynamic calculations to understand the solubility behavior of CaF₂ under different conditions. Results from the experiments and the thermodynamic calculations show that Na₂CO₃ and NaHCO₃ have similar behavior if the pH is controlled at the same value. The available carbonate (CO₃²⁻) ion in the system limits the concentration of calcium (Ca²⁺) ion by precipitation of CaCO₃, which enhances the dissolution of CaF₂. At higher temperatures and pH, calcite, vaterite, and aragonite were formed and co-precipitation of CaF₂ along with calcium carbonate (CaCO₃) was observed. At lower temperatures and lower pH levels, only calcite and vaterite were formed and a coating by CaCO₃ on CaF₂ was found to hinder complete dissolution reaction. The results of this study indicate that the temperature along with the reagents used for the dissolution tests have a significant impact on the CaCO₃ polymorph mixture (calcite, vaterite and aragonite) formation.